EP0073702B1 - Procédé de préparation de latex de polymères d'acétate de vinyle - Google Patents

Procédé de préparation de latex de polymères d'acétate de vinyle Download PDF

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Publication number
EP0073702B1
EP0073702B1 EP82401468A EP82401468A EP0073702B1 EP 0073702 B1 EP0073702 B1 EP 0073702B1 EP 82401468 A EP82401468 A EP 82401468A EP 82401468 A EP82401468 A EP 82401468A EP 0073702 B1 EP0073702 B1 EP 0073702B1
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EP
European Patent Office
Prior art keywords
weight
water
polymer
acrylamide
amide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82401468A
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German (de)
English (en)
French (fr)
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EP0073702A1 (fr
Inventor
Jean-Luc Schuppiser
Jean-Claude Daniel
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Rhone Poulenc Specialites Chimiques
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Rhone Poulenc Specialites Chimiques
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Priority to AT82401468T priority Critical patent/ATE14017T1/de
Publication of EP0073702A1 publication Critical patent/EP0073702A1/fr
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Publication of EP0073702B1 publication Critical patent/EP0073702B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/02—Esters of monocarboxylic acids
    • C08F18/04—Vinyl esters
    • C08F18/08—Vinyl acetate

Definitions

  • the subject of the invention is a process for preparing latexes of vinyl acetate polymers, as well as the latexes of polymers obtained by said process.
  • the latexes of vinyl acetate polymers are generally used as binders in the manufacture of adhesives, paints, textiles and papers. They are prepared by emulsion polymerization of vinyl acetate alone or in admixture with a copolymerizable monomer and in the presence of cellulose ethers, polyvinyl alcohols, or polyvinylpyrrolidone as protective colloids. These protective colloids give the latexes good stability in storage and handling, as well as a certain viscosity necessary for their applications, but also a sensitivity to water of the polymer films harmful to the intended applications.
  • the process which is the subject of the invention makes it possible to obtain latexes of vinyl acetate polymers which have good storage and handling stability and the viscosity necessary for their applications and whose polymer films exhibit very good resistance to the water.
  • the process according to the invention consists in polymerizing vinyl acetate in aqueous emulsion alone or in admixture with at least one copolymerizable monomer in the presence of an initiator, an emulsifier and a protective colloid and is characterized in that that the protective colloid consists of a) a water-soluble polymer of amides of acrylic and methacrylic acids and their substituted or unsubstituted N-alkylated derivatives, and b) of an ethylene glycol polymer, of molecular mass between 1,000 and 50,000, soluble in water.
  • the water-soluble amide polymer, the first constituent of the protective colloid is a homopolymer or a copolymer in all proportions or else a mixture of at least one homopolymer and / or at least one copolymer of amides of acrylic acids. and methacrylic and their N-alkylated derivatives, the alkyl group of which has 1 to 4 carbon atoms and may be substituted by amine, hydroxy or alkoxy groups having 1 to 4 carbon atoms.
  • amides may be mentioned, for example, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, N-methylaminoisopropylacrylamide, N-methylolacrylamide, N-methyloimethacrylamide , N-methoxymethylacrylamide and N-isobutoxymethylacrylamide.
  • the water-soluble amide polymer can be prepared for example by polymerization in aqueous solution of at least one amide at a concentration of 0.1 to 7% by weight, in the presence of a water-soluble radical initiator and / or of ultra-violet radiation, at a temperature between 0 and 90 ° C.
  • the initiator to be covered is a conventional water-soluble radical initiator for solution polymerization, such as hydrogen peroxide, alkaline persulfates, water-soluble diazo derivatives or redox systems based on oxidants such as hydrogen peroxide, organic peroxides or hydroperoxides and reducing agents, such as alkali sulfites and bisulfites, amines, hydrazine or metal formaldehydesulfoxylates. All these initiators are used alone or as a mixture, at a rate of 0.1 to 10% by weight of the amide (s).
  • the water-soluble amide polymer can be crosslinked by amounts of up to 50% by weight of the amide (s) of water-soluble crosslinking agents represented by N, N'-alkylidene having 1 to 4 carbon atoms bis (unsaturated acid amide having 3 to 5 carbon atoms) such as N, N'-methylene bis (acrylamide) or N, N'-methylene bis (methacrylamide), diallyl ether, diallyl sulfosuccinate or polyallylic oxyethane.
  • the amide (s) of water-soluble crosslinking agents represented by N, N'-alkylidene having 1 to 4 carbon atoms bis (unsaturated acid amide having 3 to 5 carbon atoms) such as N, N'-methylene bis (acrylamide) or N, N'-methylene bis (methacrylamide), diallyl ether, diallyl sulfosuccinate or polyallylic oxyethane.
  • the ethylene glycol polymer is soluble in water and has a molecular mass of between 1,000 and 50,000 and preferably between 3,000 and 35,000. It is represented by ethylene homopolymers glycol and mixtures of at least two homopolymers of different molecular mass. These polymers are products in themselves known and marketed.
  • the protective colloid consists of 15 to 70% by weight of the amide polymer and 30 to 85% by weight of the ethylene glycol polymer.
  • the colloid is used in an amount of 0.1 to 5% and preferably 0.5 to 3% by weight of the monomer or monomers to be polymerized.
  • the two constituents of the protective colloid are used in the form of aqueous solutions.
  • the amide polymer solution can be used at any time after its preparation, but, according to a preferred form of the invention, it is used immediately after its preparation.
  • the two solutions can be introduced separately into the emulsion polymerization medium, or the ethylene glycol polymer can be dissolved in the amide polymer solution, or alternatively, and this constitutes a preferred form of the invention, the ethylene glycol polymer can be added to the amide solution before polymerization. These introductions are carried out either all at once before polymerization, or during polymerization by successive fractions or continuously.
  • the amide polymer plus the ethylene glycol polymer represent from 0.1 to 15% by weight of the water.
  • the monomers which can be polymerized by the new process are represented by vinyl acetate alone or by vinyl acetate and at least one other copolymerizable monomer, such as vinyl esters of branched or unbranched saturated monocarboxylic acids having 1 with 12 carbon atoms, such as propionate, "Versatate” (registered trademark for mixtures of esters of branched acids in Cg to C 11 ), pivalate, vinyl laurate and / or esters of unsaturated acids mono- or di-carboxyls having 3 to 6 carbon atoms and alcohols having 1 to 10 carbon atoms, such as methyl, ethyl, butyl or ethylhexyl acrylates, methacrylates, maleates or fumarates.
  • vinyl esters of branched or unbranched saturated monocarboxylic acids having 1 with 12 carbon atoms such as propionate
  • "Versatate” registered trademark for mixtures of esters of branched acids in Cg to
  • the comonomers are used in amounts such that the glass transition temperature of the polymer obtained is between - 20 and 50 ° C and preferably between - 10 and 35 ° C.
  • the monomer (s) are introduced into the polymerization medium, either entirely before polymerization, or during polymerization by successive fractions or continuously, or partly before polymerization and the other part during polymerization by fractions successive or continuous.
  • the crosslinking monomer used in proportions of between 0 and 10% and preferably between 0 and 3% by weight relative to the monomer (s), is more particularly represented by the vinyl acrylate and methacrylate, the divinyl ether , mono- or polyalkylene (C z -C 4 ) glycol acrylates and methacrylates, allyl phthalate, triallyl cyanurate, tetraallyloxyethane, alkali diallylsulfosuccinates and carboxylic acid condensates (C 3 -C 5 ) unsaturated and polyols, such as, for example, trimethylolpropane acrylate and methacrylate.
  • the vinyl acrylate and methacrylate the divinyl ether , mono- or polyalkylene (C z -C 4 ) glycol acrylates and methacrylates, allyl phthalate, triallyl cyanurate, tetraallyloxyethane, alkali dial
  • the chain limiting agent used in proportions of between 0 and 10 and preferably between 0 and 3% by weight relative to the monomer (s), is represented, inter alia, by halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, bromoform, carbon tetrabromide, dichlorethane and trichlorethane, aliphatic alcohols having 1 to 4 carbon atoms, such as methanol and allyl alcohol, and preferably by mercaptans, such as laurylmercaptan, dodecylmercaptan and aminophenylmercaptan.
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, bromoform, carbon tetrabromide, dichlorethane and trichlorethane
  • aliphatic alcohols having 1 to 4 carbon atoms such as methanol and allyl alcohol
  • mercaptans
  • crosslinking monomer and / or the chain limiting agent are introduced alone or as a mixture, in any manner known per se, before polymerization or during polymerization, for example at the same time as the monomer (s), or simultaneously , more particularly in solution in the monomer or the mixture of monomers.
  • the concentration of monomer (s) in the polymerization medium is advantageously between 10 and 70% by weight.
  • a conventional water-soluble initiator of emulsion polymerization is used and more particularly hydrogen peroxide, alkaline persulfates, water-soluble diazo derivatives or redox systems based on oxidants such as hydrogen peroxide, peroxides or organic hydroperoxides and reducing agents such as alkali sulfites and bisulfites, amines, hydrazine or metal formaldehydesulfoxylates.
  • the initiator is used in proportions of the order of 0.05 to 4.5% and preferably 0.1 to 2% by weight of the monomer (s).
  • one or more emulsifying agents may or may be present in the reaction medium.
  • the emulsifying agents can be anionic and / or nonionic and are conventional products of emulsion polymerizations.
  • anionic emulsifying agents there may be mentioned the fatty acid salts; alkylsulfates, alkylsulfonates, alkylarylsulfonates, alkylsulfosuccinates, alkaline alkylphosphates; sulfonates of alkylphenolpolyglycolic ethers; ester salts of alkylsulfopolycarboxylic acids; the condensation products of fatty acids with oxy- and amino-alkanesulfonic acids; sulfated derivatives of polyglycolic ethers; sulfated esters of fatty acids and polyglycols; alkanolamides of sulfated fatty acids.
  • nonionic emulsifying agents the fatty esters of polyalcohols, the alkanolamides of fatty acids, the copolyoxides of ethylene and propylene, the oxyethylenated alcohols and alkylphenols, the oxyethylenated and sulfated alcohols and alkylphenols are to be mentioned.
  • the amounts of emulsifying agent (s) to be used are of the order of 0.1 to 3% by weight relative to the monomer (s) and their introduction into the reaction medium can be carried out either entirely before the polymerization, or partly before the polymerization, the additional part being added to the reaction medium during the polymerization by successive fractions or continuously, or again entirely during the polymerization by successive fractions or continuously, depending on the average diameter of the latex particles to be obtained.
  • the emulsifying agent is added to the preparation medium of the amide polymer, the first constituent of the protective colloid.
  • the polymerization medium may be advantageous to maintain the polymerization medium at a pH of 3 to 7.
  • a pH regulator represented in particular by a base, such as sodium hydroxide or ammonia and / or by a buffer, such as sodium acetate, sodium bicarbonate or borax.
  • the regulator is added to the medium, alone or as a mixture, in whole or in part before the polymerization, the additional part being added during the polymerization by successive fractions or continuously, or even completely during the polymerization by successive fractions or continuously and more particularly in the medium for preparing the amide polymer, the first constituent of the protective colloid.
  • the polymerization temperature is generally between 0 and 95 ° C and preferably between 20 and 90 ° C.
  • the method, as described above, is carried out in the presence of a seed polymer, which ensures better control of the particle size of the latex particles to be obtained.
  • This seed polymer may be similar or different from the polymer to be obtained. It is obtained by aqueous emulsion polymerization of vinyl acetate and / or at least one of the comonomers listed above.
  • the seed polymer latex obtained is added to the polymerization medium at the same time as one of the constituents of the protective colloid or at the same time as the mixture of these two constituents, or else is prepared in the presence of one of these constituents or two constituents of the protective colloid.
  • a plasticizing agent in proportions of between 0 and 20% and preferably between 0 and 10% by weight relative to the polymer.
  • This plasticizing agent used alone or as a mixture, is chosen from plasticizers and conventional coalescing agents of polyvinyl acetate, such as halogenated or nonhalogenated alkyl phthalates (C 4 -Ce), such as dibutyl phthalates , diethyl and trichlorethyl, phthalate, adipate and ethylene glycol dibenzoate, butylcarbitol acetate, butyl glycolate, glycerol triacetin, succinates, glutarates, dipropylic or diisobutyl adipates and tricresyl and triphenyl.
  • C 4 -Ce halogenated or nonhalogenated alkyl phthalates
  • the polymer latexes obtained have a concentration of 10 to 70% and preferably 35 to 65% by weight of polymer particles having a glass transition temperature between - 20 and 50 ° C, whose narrow or spread particle size is between 0.05 and 1 ⁇ m.
  • the latexes have a wide range of viscosity ranging from a few mPa - s to 80,000 mPa - s and preferably from 50 to 30,000 mPa s, and give films having very good water resistance.
  • Latexes are used as binders in the manufacture of paints, glues, papers, textiles, especially nonwovens, floor coverings, additives for mortars.
  • the air is removed by passing a stream of nitrogen, which is maintained and the mixture is stirred. After dissolution, the solution is heated to 60 ° C.
  • reaction mixture After 15 minutes from the start of the introduction, the reaction mixture is heated to 80 ° C., then maintained at this temperature and 2 g of ammonium persulfate in 200 g of water are introduced continuously at constant rate over 2 h 45 min.
  • reaction mixture is cooled.
  • Example 1 is repeated, replacing the 13.5 g of acrylamide with 6.5 g of acrylamide, 6 g of methacrylamide and 1 g of acrylic acid. From the start of the polymerization of vinyl acetate, grains are formed in the reaction medium, which is completely coagulated at the end of the introductions. The product obtained is unusable.
  • the polyethylene glycol is added to the medium before polymerization of the vinyl acetate, instead of being added to the preparation of the colloid, there is formation of crusts on the walls of the polymerization reactor and on the 'stirrer.
  • the latex obtained contains grains and its viscosity is low, which gives, in applications, properties much lower than those obtained with the latex of Example 1.
  • VEOVA 10 is a mixture of Cg to C 11 branched monocarboxylic vinyl esters.
  • a vinyl acetate / "Versatate VEOVA 10" ® 75/25 copolymer prepared in the presence of polyvinylpyrrolidone in an amount equal to that of the protective colloid of Example 2 has a water resistance of 30 s.
  • the air is removed by passing a stream of nitrogen, which is maintained and the mixture is stirred. After dissolution, the solution is heated to 60 ° C.
  • reaction mixture After 15 minutes from the start of the introduction, the reaction mixture is heated to 80 ° C., then maintained at this temperature and 2 g of ammonium persulfate in 200 g of water are introduced continuously at constant rate over 2 h 45 min.
  • reaction mixture is cooled.
  • the air is removed by passing a stream of nitrogen which is maintained during the preparation of the colloid.
  • the mixture is stirred.
  • the solution is heated to 60 ° C, which temperature is maintained.
  • reaction medium After 20 minutes, the reaction medium is heated to 80 ° C., maintained at this temperature for 1 hour, then cooled to room temperature.
  • the mixture is stirred and heated to 80 ° C., a temperature which is maintained for the duration of the reaction.
  • the air is removed by passing a stream of nitrogen, which is maintained and the mixture is stirred. After dissolution, the solution is heated to 60 ° C.
  • reaction mixture After 15 minutes from the start of the introduction, the reaction mixture is heated to 80 ° C., then maintained at this temperature and 2 g of ammonium persulfate in 200 cm 3 of water are introduced continuously at constant rate over 2 h 45 mins.
  • reaction mixture is cooled.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Sealing Material Composition (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Graft Or Block Polymers (AREA)
  • Paper (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Cephalosporin Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP82401468A 1981-08-10 1982-08-04 Procédé de préparation de latex de polymères d'acétate de vinyle Expired EP0073702B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82401468T ATE14017T1 (de) 1981-08-10 1982-08-04 Verfahren zur herstellung eines latex von vinylacetat-polymeren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8115436A FR2511008B1 (fr) 1981-08-10 1981-08-10 Procede de preparation de latex de polymeres d'acetate de vinyle
FR8115436 1981-08-10

Publications (2)

Publication Number Publication Date
EP0073702A1 EP0073702A1 (fr) 1983-03-09
EP0073702B1 true EP0073702B1 (fr) 1985-06-26

Family

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Family Applications (1)

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EP82401468A Expired EP0073702B1 (fr) 1981-08-10 1982-08-04 Procédé de préparation de latex de polymères d'acétate de vinyle

Country Status (14)

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US (1) US4440896A (el)
EP (1) EP0073702B1 (el)
JP (1) JPS5837013A (el)
AT (1) ATE14017T1 (el)
BR (1) BR8204665A (el)
CA (1) CA1186837A (el)
DE (1) DE3264421D1 (el)
DK (1) DK355982A (el)
ES (1) ES514838A0 (el)
FI (1) FI70907C (el)
FR (1) FR2511008B1 (el)
GR (1) GR78000B (el)
MA (1) MA19567A1 (el)
NO (1) NO822266L (el)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1092430A (zh) * 1989-10-25 1994-09-21 陶氏化学公司 纸张涂料组合物用的胶乳共聚物
CN1072689A (zh) * 1991-11-27 1993-06-02 罗姆和哈斯公司 降低胶乳膨胀性的方法
DE4324474A1 (de) * 1993-07-21 1995-01-26 Henkel Kgaa Verwendung ausgewählter Polyvinylacetat-Dispersionen für die Oberflächenverfestigung von Sand und/oder Erdreich
CA2128296A1 (en) * 1993-12-22 1995-06-23 Peter John Degen Polyvinylidene fluoride membrane
WO1997025470A1 (en) * 1996-01-05 1997-07-17 Reichhold Chemicals, Inc. Textile latex
DK1325044T3 (da) * 2000-09-29 2004-10-04 Basf Ag Vandig dispersion af vinylacetatpolymer

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2998400A (en) * 1958-05-15 1961-08-29 Wyandotte Chemicals Corp Floc-free polyvinyl acetate emulsions employing polyvinylmethyl ether copolymer as prtective colloid and process of preparation
NL292308A (el) * 1962-05-05
DE1301064B (de) * 1965-05-13 1969-08-14 Basf Ag Verfahren zur Herstellung waessriger Dispersionen von Vinylesterpolymerisaten
FR1479750A (fr) * 1965-05-13 1967-05-05 Basf Ag Procédé de préparation de dispersions aqueuses de polymères d'esters vinyliques
JPS57138059A (en) * 1981-02-20 1982-08-26 Matsushita Electric Ind Co Ltd Manufacture for magnetic recording medium

Also Published As

Publication number Publication date
ATE14017T1 (de) 1985-07-15
FI70907B (fi) 1986-07-18
FI70907C (fi) 1986-10-27
FR2511008B1 (fr) 1985-10-04
EP0073702A1 (fr) 1983-03-09
FI822788L (fi) 1983-02-11
NO822266L (no) 1983-02-11
FR2511008A1 (fr) 1983-02-11
BR8204665A (pt) 1983-08-02
ES8401991A1 (es) 1984-01-01
GR78000B (el) 1984-09-26
MA19567A1 (fr) 1983-04-01
FI822788A0 (fi) 1982-08-10
ES514838A0 (es) 1984-01-01
JPS5837013A (ja) 1983-03-04
US4440896A (en) 1984-04-03
JPS6244002B2 (el) 1987-09-17
DK355982A (da) 1983-02-11
CA1186837A (fr) 1985-05-07
DE3264421D1 (en) 1985-08-01

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